World No.22 Makarova put her close friendship with Zvonareva to one side and needed only 63 minutes to finish offer the two-time champion for a quarter-final spot in the WTA event.
A wildcard, Zvonareva, who won in Pattaya in 2009 and 2010, could not handle Makarova's powerful groundstrokes in only her third event back after 17 months out with a shoulder injury.
Zvonareva began her comeback this month in Shenzhen and played in the Australian Open but lost her first matches at both tournaments.
She is currently No.992 in the rankings, having once been at No.2.
''I was out for a year and had surgery which makes it difficult to come back,'' said an emotional Zvonareva at the post-match press conference.
''It is a challenge for me. I have to keep on working hard to get back.''
Zvonareva and her Thai partner Noppawan Lertcheewakarn will play in the doubles on Thursday.
Makarova said: ''Vera is my good friend so it is difficult for me to play against her. I think Vera can come back to her top form. She is a great player and had many good results in the past.''
Makarova will next play today's winner between Japanese veteran Kimiko Date-Krumm and Tadeja Majeric of Slovenia.
In yesterday's doubles event, Nicha Lertpitaksinchai and Peangtarn Plipuech lost to Eleni Daniilidou of Greece and Aleksandra Krunic of Serbia 6-4, 2-6, 9-11.
Nicha, the only Thai left in the singles, will meet fifth seed Elena Vesnina of Russia in the second round on Thursday.
''It will be a tough match for me. I watched her play yesterday - she has strong groundstrokes and her serve is very good,'' Nicha said. ''I will be the underdog but I will do my best.''
Ekaterina Makarova (4xRUS) beat Vera Zvonareva (RUS) 6-0, 6-2; Karolina Pliskova (CZE) beat Alla Kudryavtseva (RUS) 4-6, 6-3, 6-4; Sorana Cirstea (3xROM) beat Alison Riske (USA) 6-3, 6-4
Eleni Daniilidou (GRE)/Aleksandra Krunic (SRB) beat Nicha Lertpitaksinchai/Peangtarn Plipuech (THA) 4-6, 6-2, 11-9; Shuai Peng/Shuai Zhang (CHN) beat Shuko Aoyama (JPN)/Alesandra Dulgheru (ROU) 6-3, 6-3; Chia-Jung Chuang (TPE)/Luksika Kumkhum (THA) beat Varatchaya and Varunya Wonteanchai (THA) 6-1, 6-3
TODAY ORDER OF PLAY
Court 1 (3pm)
Tadeja Majeric (SLO) vs Kimiko Date-Krumm (JPN); Elena Vesnina (RUS) vs Nicha Lertpitaksinchai (THA); Alexandra Dulgheru (ROU) vs Shuai Peng (CHN)
Court 2 (3pm)
Noppawan Lertcheewakarn/Vera Zvonareva vs Eleni Daniilidou/Aleksandra Krunic; Chia-Jung Chuang/Luksika Kumkhum or Varatchaya Wongteanchai/Varunya Wongteanchai vs Andrea Hlavackova/Anabel Medina Garrigues; Kimiko Date-Krumm/Ajla Tomljanovic vs Paula Kania/Valenria Solovyeva or Alla Kudryavtseva/Anastasia Rodionova